WO2002030824A1 - Vanadium oxide hydrate compositions - Google Patents
Vanadium oxide hydrate compositions Download PDFInfo
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- WO2002030824A1 WO2002030824A1 PCT/US2000/027660 US0027660W WO0230824A1 WO 2002030824 A1 WO2002030824 A1 WO 2002030824A1 US 0027660 W US0027660 W US 0027660W WO 0230824 A1 WO0230824 A1 WO 0230824A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/006—Compounds containing, besides vanadium, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- This invention pertains to new vanadium oxide hydrate compositions highly suitable for use as electrode-active materials in primary and secondary lithium and lithium ion batteries, and processes for their preparation.
- vanadium oxide hydrates generally described by the formula V2 ⁇ 5 » nH2 ⁇ , have generally not exhibited the combination of high lithium ion insertion capacity, low hysteresis in charge/discharge cycles, high power density, and low sensitivity to discharge rate which is required for practical use in rechargeable, or "secondary", lithium batteries.
- Le et al. U.S. Patent 5,674,642 has disclosed a fibrous V2 ⁇ 5 # nH2 ⁇ composition with sufficiently high litluum insertion capacity to make it a practical choice for an electrode active material in lithium batteries. Similar fibrils and ribbons formed according to the process of Le et al. disclosed in S. Passerini et al., Electrochimica Acta, Vol. 44, 1999, pp. 2209-2217, and J. Livage, Chem. Mater. Vol. 3, 1991, pp. 578-593.
- the present invention provides for a process for producing MxV2 ⁇ 5Ay » nH2 ⁇
- M is selected from the group consisting of NH4 + , Na + , K + , Rb + , Cs + , and Li +
- A is selected from the group consisting of NO3-, SO -2 , and Cl ⁇ ; 0 ⁇ x ⁇ 0.7, and 0 ⁇ y ⁇ 0.7; and, 0.1 ⁇ n ⁇ 2, the process comprising combining a water-soluble vanadate salt with water to form a solution; and, adding to said solution a strong inorganic acid such that the molar ratio of acid protons to vanadium is in the range of 0.70:1 to 6:1.
- the present invention provides for an electrode-active material composition
- an electrode-active material composition comprising non-fibrous MxV2 ⁇ 5Ay*nH2 ⁇ wherein M is selected from the group consisting of NH 4 + , Na + , K + , Rb + , Cs + , and Li + ; A is selected from the group consisting of NO 3 -, SO4" 2 , and Cl ⁇ ; 0 ⁇ x ⁇ 0.7, and 0 ⁇ y ⁇ 0.7; and, 0.1 ⁇ n ⁇ 2, the process comprising 0.1 ⁇ n ⁇ 2.0, said electrode-active material composition being characterized by an initial discharge capacity of 315 to 400 mAh/per gram of electrode-active material composition.
- an electrode composition comprising the electrode-active material composition of the invention.
- Electrode composition comprising the electrode-active material composition of the invention.
- Figure 1 represents a graphical depiction of the initial discharge capacity determined in Examples 1-16 as a function of H/N ratio.
- Figures 2a and 2b depict scanning electron micrographs at magnifications of 10,000 and 30,000 respectively of the non-fibrous product of Example 10.
- Figures 3 a and 3b depict scanning electron micrographs at magnifications of 10,000 and 30,000 respectively of the non-fibrous product of Example 16.
- Figures 4 and 5 depict the initial discharge curve and first re-charge curve showing milliamp-hours per gram of electrode-active material versus voltage as determined in Examples 10 and 16 respectively.
- the present invention is directed to a process for forming a highly purified, non-fibrous form of V2 ⁇ 5 » nH2 ⁇ wherein 0.1 ⁇ n ⁇ 2 which is highly suitable for use as an electrode-active material in batteries, particularly lithium and lithium ion primary and secondary batteries, and to the compositions, electrodes, and electrochemical cells formed therewith. It is found in the practice of the process of the invention that the V2 ⁇ 5 » nH2 ⁇ formed thereby normally exhibits a degree of contamination from residual cation of the vanadate salt and residual anion from the strong acid employed in the process of the invention. This residue does not affect the suitability of V2 ⁇ 5 » nH2 ⁇ of the invention for its intended use.
- the product of the process of the present invention is more properly designated by the formula MxV2 ⁇ 5AynH2 ⁇ wherein M is selected from the group consisting of NH4 + , Na + , K + , Rb + , Cs + , and Li + ; A is selected from the group consisting of NO3", SO4- 2 , and C1-; 0 ⁇ x ⁇ 0.7, and 0 ⁇ y ⁇ 0.7; and 0.1 ⁇ n ⁇ 2.
- M is selected from the group consisting of NH4 + , Na + , K + , Rb + , Cs + , and Li +
- A is selected from the group consisting of NO3", SO4- 2 , and C1-; 0 ⁇ x ⁇ 0.7, and 0 ⁇ y ⁇ 0.7; and 0.1 ⁇ n ⁇ 2.
- x and y are as close to zero as possible, but in practice they usually are about 0.2.
- nH2 ⁇ the term 'N2 ⁇ 5 » nH2 ⁇ " will be employed as a shorthand to indicate the product of the process of the present invention to encompass the full range of the values of both x and y, namely 0 to 0.7.
- a water soluble vanadate salt is dissolved in water preferably accompanied by heating, followed by precipitation at high yield of the desired V2 ⁇ 5*nH2 ⁇ product.
- the resulting product exhibits a non-fibrous morphology, and is characterized by a surprisingly high initial discharge capacity in a standard lithium battery test cell with very high reversibility.
- initial discharge capacity refers to the electrical discharge capacity of a standard lithium metal cell in which the V2 ⁇ 5 *nH2 ⁇ compositions of the invention have been incorporated as the electrode-active cathode material.
- the "initial discharge capacity" determined in a standardized configuration is believed to be a relative indicator of the inherent lithium ion insertion capacity of the V2 ⁇ 5*nH2 ⁇ compositions of the invention.
- initial discharge capacity is determined as follows: the V2 ⁇ 5 » nH 2 O of the invention is combined with carbon black and a binder resin as in the various embodiments hereinbelow described to form an electrode ink or paste.
- the electrode ink or paste so-formed is combined in a standard lithium metal coin cell configuration described hereinbelow.
- the coin cell so formed is in the charged state.
- the cell is then subject to discharging over the range of 4-1.5 volts while voltage (V) and current (I) are measured as a function of time.
- the measurement of initial discharge capacity begins with a constant current discharge at 0.5 ma.
- the discharge mode is changed to constant voltage wherein the voltage is held constant while the current slowly decays to 1/10 th the original value, i.e., 0.05 ma.
- This constant voltage portion of the discharge which allows the cell to nearly reach equilibrium, has the effect of reducing the potential drops from the current so that the remaining cell polarization is principally due to the over potential required for lithium insertion into the cathode material.
- the initial discharge capacity is the integrated charge transfer during both the constant current and constant voltage portion of the discharge. For performing these measurements, it has been found suitable to employ a Maccor series 4000 tester (Maccor, Inc., Tulsa, Oklahoma) using channels with a 10 ma maximum current capability and Version 3.0 (SP1) software.
- water preferably deionized water
- a vanadate salt preferably ammonium, alkali, and alkaline earth vanadates such as NH4VO3, L1NO3, ⁇ aVO 3 , KVO3, RbVO 3 , CsVO 3 , and MgV 2 O 6 .
- Preferred are NH4VO3, L1VO3, KVO3, MgV 2 O 6 .
- V2O5 can be combined with aqueous ammonium, alkali, or alkaline earth hydroxide in stoichiometric quantities to form in situ the corresponding vanadate solution. Most preferably the solution is heated to its boiling point.
- H/V ratio (designated the "H/V ratio" hereinafter) in the range of about 0.70:1 to 6:1.
- Suitable acids for the practice of the invention include H2SO4, HNO3, HC1, or other strong acid, except phosphorus-containing acids which will undesirably form vanadium phosphate side products.
- vanadate salts of NH4 and Rb, and probably Na, K, and Cs the acid vanadium ratio must be high enough, typically at least 1:1, to avoid or minimize the co-formation of M2N6O16. Acids may be incorporated in concentrated or dilute form, with the dilute form preferred for safety.
- V2 ⁇ 5 » nH2 ⁇ precipitate may be recovered by any convenient method including settling followed by decanting the supernatant liquid, filtration, centrifugation and so forth.
- the precipitate is characterized by a non-fibrous morphology and a contamination level of less than about 15%, normally less than about 4%.
- the dissolution of the vanadate salt in the water maybe accomplished in most cases at any convenient temperature including room temperature, but it is found in the practice of the invention that the rate of dissolution is quite slow at room temperature, and is greatly increased by heating, particularly to a temperature at or near the boiling point. At temperatures below the boiling point, dissolution is considerably enhanced by agitation.
- Precipitation of the V2 ⁇ 5 » nH2 ⁇ of the invention by acid addition to the vanadate salt solution may be accomplished at any convenient temperature including room temperature.
- it is found in the practice of the invention that it is highly desirable to effect the reaction at elevated temperature, particular in the range from 80°C to the boiling point of the solution. Effecting the reaction at the boiling point is most preferred. It is found in the practice of the invention that both reduced yield and reduced product quality or performance are likely to result when the temperature of reaction is below 80°C.
- the recovered solid be re-slurried with fresh water to remove contaminants, followed by once again recovering the solid.
- the recovered solid is then dried by any convenient means including but not limited to radiative warming and oven heating. Following drying, pulverization, and sieving, the V2 ⁇ 5 , nH2 ⁇ so produced is ready for incorporation into an electrode composition.
- the resulting precipitate is a non-fibrous form of V2 ⁇ 5 « nH2 ⁇ with a high initial discharge capacity.
- the percentage of the dissolved vanadium precipitated which largely determines the single pass product yield, is largely determined by the H/N ratio, with the highest yield achieved at H/N ratios of about 1:1 to 2:1.
- non-fibrous is meant not having a microstructure consisting of fibers or ribbons as revealed by scanning electron microscopy at magnifications of about 30,000x.
- Figures 2a and 2b depict scanning electron micrographs of the specimen of Example 10 herein at magnifications of 10,000 and 30,000 respectively;
- Figure 3 a and 3b represent similar micrographs for the coated-on- carbon specimen of Example 16 herein.
- the non-fibrous N2O5M1H2O made by the process of the invention is characterized by markedly higher initial discharge capacity than V2 ⁇ 5 » nH2 ⁇ made by a vanadium salt acid precipitation process outside the H/N ratio limits of the process of the invention.
- This is shown in Figure 1 wherein the initial discharge capacity is shown as a function of H/V ratio for the specific embodiments hereinbelow exemplified.
- the optimum H/N ratio is achieved at H/N ratios of about 1.5 : 1 to 2.5 : 1.
- Examples 10 and 16 represent the same synthesis with the difference being that Example 16 involved a coated-carbon composition and Example 10 did not.
- the polarization of the coated carbon specimen was less than that of the N2 ⁇ 5*nH2 ⁇ specimen not coated onto carbon, as indicated by the closer proximity of the curves in the low- voltage region. This beneficial effect of the coated-carbon compositions becomes considerably more pronounced with increasing rate of discharge and charge.
- Cycle life is defined as the number of cycles of charging and discharging cycles to which the test coin cell can be subject before the discharge capacity decreases to 80% of its initial value. It is believed by the inventor hereof that cycle life achieves an optimum value at an H/N ratio of about 4. That is to say that there appears to be some trade-off between yield and initial discharge capacity on the one hand, and cycle life on the other. It is further found in the practice of the invention that the initial discharge capacity depends upon the cation of the vanadium salt employed in the process of the invention. The highest initial discharge capacity is achieved when the V 2 O5'nH 2 O is produced from NH4VO3, LiVO 3 , or MgV 2 O 6 .
- elemental carbon for example carbon black
- the carbon black is slurried into the vanadium salt solution prior to the addition of the acid.
- the carbon black may be added to the water before the vanadium salt is dissolved therein, simultaneously with the dissolution of the vanadium salt, or after the dissolution of the vanadium salt.
- the resulting precipitation product after acid addition in the manner hereinabo ve described is a finely dispersed powder of carbon black coated with V2 ⁇ 5 » nH2 ⁇ which is highly preferred for use in secondary or rechargeable lithium batteries.
- the coated carbon black product exhibits the high initial discharge capacity characteristic of the V2 ⁇ 5*nH2 ⁇ , with low polarization, high capacity retention at high discharge rates, and high vanadium utility or energy efficiency.
- the amount of carbon black found suitable for the practice of the invention is of an amount ranging from 1-12%, preferably 4-8%, by weight on the weight of the total weight of the final isolated carbon- V 2 O5 '10120 dried powder. 1-12% by weight correspond to a carbon-vanadium mole ratio of about 0.1-1.2 when n ⁇ l .2, a preferred value. Any form of finely dispersed elemental carbon is suitable for the practice of the invention.
- Super P carbon black commercially available from MMM S.A.
- Carbon, Brussels, Belgium, is one such suitable elemental carbon which has a surface area of about 62 m 2 /g. While no particular limitations on surface area have been determined for the carbon black suitable for use in the present invention, it is believed that higher surface areas are preferred over lower surface areas.
- the carbon black is first slurried separately in aqueous dispersion, and the resulting slurry is added to the heated vanadate solution.
- the process of the invention may be performed in both batch and continuous modes.
- a continuous process, with a recycle stream of unprecipitated vanadate salt, is particularly desirable when the reaction is run under relatively low-yield conditions.
- an electrode composition by combining an electrode-active material, such as the V2 ⁇ 5 # nH2 ⁇ of the invention, with carbon black and a binder resin to provide improved electronic conductivity as well as superior physical integrity to the electrode composition.
- an electrode-active material such as the V2 ⁇ 5 # nH2 ⁇ of the invention
- carbon black and a binder resin to provide improved electronic conductivity as well as superior physical integrity to the electrode composition.
- 8% by weight of carbon black represents a typical practical maximum carbon black concentration because amounts in excess of 8% often cause the electrode composition to become undesirably intractable and brittle.
- the present invention solves the problem of incorporating additional elemental carbon into the composition with minimum deleterious effects on the physical integrity of the electrode composition formed according to the practice hereof.
- a preferred electrode composition of the invention comprises a V2 ⁇ 5 » nH2 ⁇ -coated carbon black composition incorporating 8% carbon black formed according to the process of the invention as hereinabove described. That composition can be combined according to the teachings of the art with an additional 8% of carbon black and a binder resin to form a tough, formable electrode composition with 16% carbon black and the improved electrochemical performance expected from the higher overall carbon black concentration in the electrode composition.
- Suitable binder resins include EPDM rubber, polyvinylidene fluoride and its copolymers for example with hexafiuoropropylene as well as other resins such as are known in the art as suitable for the purpose. Binder resins are normally first dissolved in fugitive solvents before combining with the other ingredients of the electrode. Suitable solvents are well known in the art and include acetone, cyclohexane, and cyclopentanone, among others. Not all binders suitable for the practice of the invention required dissolution in a solvent.
- the electrode composition of the invention comprising elemental carbon coated with V 2 ⁇ 5*nH2 ⁇ exhibits considerable benefits over a similar electrode composition comprising
- V2 ⁇ 5 » nH2 ⁇ of the invention when the V 2 ⁇ 5 » nH2 ⁇ is not coated onto elemental carbon.
- These benefits include reduced polarization on charge/discharge cycles, higher initial discharge capacity per gram of vanadium, and much lower reduction in initial discharge capacity with increasing rate of discharge.
- the process of the invention for producing V2 ⁇ 5 , nH 2 O-coated carbon may also be employed to add or dope in other elements.
- M x B z V2 ⁇ 5A •11H2O
- A is an anion derived from the acid
- y 0.0-0.7
- B is a transition, main group, or rare-earth metal
- z 0.0-1.0
- n 0.1-2.0.
- Lithium-ion cells may also be formed according to the process of the invention, and may be preferred in numerous applications.
- a lithium-ion battery is assembled in the charged state by either using an anode material which contains already the appropriate cyclable lithium or some fraction thereof. This may be achieved as is known in the art, for example, by contacting lithium metal or some other lithium source with a carbon-based anode material during cell assembly which will allow the necessary cyclable lithium to be accommodated in the carbon structure.
- Another means for using the claimed materials in lithium-ion cells would involve intentional prelithiation of the vanadium oxide hydrates for example by either chemical means or electrochemical means. This would increase the lithium content in the claimed materials to desirably higher levels for use in lithium-ion batteries with initially discharged anodes.
- An example of a lithium ion cell is provided in Example 17.
- EXAMPLE 1 18.2 g L1VO3 were added to about 450 ml deionized H2O while stirring with a Teflon coated magnetic stirring bar in a 1 liter Pyrex beaker. The contents of the beaker were heated to the boiling point to form a solution. With stirring, 7.5 ml of concentrated HNO3 were added to the boiling solution. The resulting solution was continued at the boil while stirring for 5 minutes. The H/V ratio was 0.7.
- the powder was sieved through a 200 mesh screen to get powder suitable for making a cathode.
- 1.5000 g of the powder were combined with 0.1364 g of Super P carbon black commercially available from MMM S.A. Carbon, Brussels, Belgium, and 1.705 g of a 4 wt % solution of EPDM rubber in cyclohexane. 2.5 ml extra cyclohexane were added to improve flow.
- the mixture was shaken in a capped glass vial for 15 minutes on a mechanical shaker to form a cathode paste.
- the cathode paste was spread onto a sheet of Teflon® FEP (E. I. du Pont de Nemours and Company, Wilmington DE) and drawn down to form a film using a doctor blade having a 15 mil gap.
- Teflon® FEP E. I. du Pont de Nemours and Company, Wilmington DE
- the dried film consisting of 88% by weight powder, 4% by weight binder, and 8% by weight carbon black, was hot-pressed through a calendar roller between Kapton® polyimide sheets (DuPont) at 2000 psi and 110°C to form a consolidated electrode sheet suitable for use as a cathode in a lithium battery.
- the thickness of the sheet was 115 micrometers.
- the resultant consolidated electrode sheet was employed as a cathode against a Li metal anode in an electrochemical cell.
- LiPFg in EC/DMC ethylene carbonate/dimethyl carbonate
- a glass fiber separator was used between the electrodes. Disks of cathode, anode, and separator were cut with punches. In a dry nitrogen atmosphere, the cathode and separator pieces were soaked in electrolyte solution, then stacked along with the Li into a coin-cell pan and sealed under pressure using the 2325 Coin Cell Crimper System manufactured by the National Research Council of Canada. The coin cell was tested as described above and the initial discharge capacity was determined to be 315 mAh/g.
- EXAMPLE 2 15.6 g of anhydrous V2O5 and 7.2 g of LiOH ⁇ O were combined with 900 ml of deionized water and treated as in Example 1 to form V2 ⁇ 5 # nH2 ⁇ , except that dilute H2SO4, made by combining 3.6 ml of concentrated H2SO4 with 40 ml H2O, was added to the boiling solution, the duration of heating after acid addition was 35 minutes. The H/V ratio was 0.75.
- the beaker was then removed from the heat and stirring discontinued.
- the unwashed gelatinous solid which did not settle after one hour, was collected on filter paper by suction filtration.
- the product filtered very slowly and the filtrate was orange in color indicating the presence of a considerable amount of unprecipitated vanadium.
- the pH of the filtrate measured with multi-color strip pH paper, was about 3.
- the filter cake was spread onto a large cover glass and dried at room temperature for four days and under an IR heat lamp for 2 hours, yielding 12.5 grams of dried powder.
- An impurity phase believed to be
- Li2S ⁇ 4 » H2 ⁇ was seen in x-ray powder diffraction.
- a nonreactive impurity has the effect of diluting the active material and lowering the overall Li insertion capacity.
- a product yield of 65% was estimated.
- Example 2 The resulting dried powder of V2 ⁇ 5 » nH2 ⁇ was then processed and combined as described in Example 1 to form an electrode 108 micrometers thick, which was incorporated into a coin cell as in Example 1, and the initial discharge capacity found to be 265 mAh/g.
- EXAMPLE 3 18.2 g of L1VO3 were combined with 900 ml of deionized water and treated as in Example 1 to form V2 ⁇ 5 , nH 2 O, except that dilute H2SO4, made by combining 4.8 ml of concentrated H2SO4 with 20 ml H2O, was added to the boiling solution, the duration of heating after acid addition was 15 minutes. The H/V ratio was 1.0.
- the beaker was then removed from the heat and stirring discontinued. Solids were allowed to settle until the beaker was cool to the touch. About 400 ml of supernatant liquid were decanted. The decanted supernatant liquid was pale yellow in color indicating the presence of some unprecipitated vanadium. About 400 ml of fresh H 2 O were added to the precipitate in the beaker, which was then slurried with the water by stirring for about one minute. The precipitate was allowed to settle for 10 minutes, and about 500 ml of the supernatant liquid was decanted. About 500 ml fresh H2O was added, and slurried for one minute. The precipitate was allowed to settle for about 20 minutes and again the supernatant liquid was decanted.
- the solid was collected on filter paper by suction filtration.
- the pH of the filtrate measured with multi-color strip pH paper, was about 3.
- the filter cake was spread onto a large cover glass and dried under an IR heat lamp, yielding 17.2 grams of dried powder.
- A was derived from chemical and thermogravimetric analyses. On the basis of this composition, a product yield of 97% was calculated.
- An X-ray powder diffraction pattern showed only the lines of V2 ⁇ 5 » nH2 ⁇ .
- Example 2 The resulting dried powder of V 2 O5 nH 2 O was then processed and combined as described in Example 1 to form an electrode 115 micrometers thick, which was incorporated into a coin cell as in Example 1, and the initial discharge capacity found to be 355 mAh/g.
- EXAMPLE 4 50.0 g of anhydrous V2O5 and 23.1 g of LiOH- ⁇ O were combined with 350 ml of deionized water in a 600 ml Pyrex beaker and stirred with a Teflon coated magnetic stirring bar and heated to about 80°C to form a solution. With stirring, 50 ml of concentrated HC1 were added to the hot solution. The H/N ratio was 1.1. After 15 minutes, the heating and stirring were discontinued, and the slurry cooled to room temperature. The solid was collected on filter paper by suction filtration.
- the beaker was then removed from the heat and stirring continued until the beaker was cool to the touch. After collecting the solid on filter paper by suction filtration, the wet solid was slurried in 350 ml of fresh deionized water by stirring with a magnetic stir bar for 1 minute, then collected as before. The solid was again slurried with a fresh 350 ml portion of water and collected as before.
- the pH of the filtrate was now about 3.
- the filter cake was dried in air at 110°C.
- EXAMPLE 7 20.1 g of NH4VO3 were combined with 900 ml of deionized water and treated as in Example 5 to form V2 ⁇ 5*nH2 ⁇ , except that the duration of heating after acid addition was 20 minutes. The beaker was then removed from the heat and stirring discontinued. The solids settled quickly and were allowed to settle for 5 minutes. About 600 ml of supernatant liquid were decanted. The decanted supernatant liquid was pale yellow in color indicating the presence of some unprecipitated vanadium. About 700 ml of fresh H 2 O were added to the precipitate in the beaker, which was then slurried with the water by stirring for about one minute.
- the precipitate was allowed to settle for.10 minutes, and about 700 ml of the supernatant liquid were decanted. About 700 ml fresh H2O were added, and slurried for one minute. The precipitate was allowed to settle for about 20 minutes and again the supernatant liquid was decanted. The pH of the supernatant liquid was about 2.
- the product was easily and quickly collected on filter paper by suction filtration. The moist cake was crumbled onto a large cover glass and dried in air at room temperature for 3.5 days to give 15.8 grams of material. The voluminous product was easily powdered in a mortar.
- Example 2 The resulting dried powder of V2 ⁇ 5 » nH2 ⁇ was then processed and combined as described in Example 1 to form an electrode 130 micrometers thick, which was incorporated into a coin cell as in Example 1, and the initial discharge capacity found to be 370 mAh/g.
- EXAMPLE 8 8.2 g of NH4VO3 were combined with 150 ml of deionized water and treated as in Example 1 to form N2 ⁇ 5 » nH2 ⁇ , except that 6.6 ml concentrated H ⁇ O3 were added, the duration of heating after acid addition was 2 minutes and the H/N ratio was 1.5.
- the beaker was then removed from the heat and stirring continued until the beaker was warm to the touch.
- the product was easily and quickly collected on filter paper by suction filtration.
- the unwashed cake was dried overnight under an infrared heat lamp. was derived from a thermogravimetric analysis. An X-ray powder diffraction pattern showed only the lines of V2 ⁇ 5 *nH2 ⁇ .
- the resulting dried powder of V2 ⁇ 5 *nH2 ⁇ was then processed and combined as described in Example 1, except the amounts of active material, EPDM binder, and carbon black, were 90%, 2%, and 8% by weight, respectively, to form an electrode 120 micrometers thick, which was incorporated into a coin cell as in Example 1, and the initial discharge capacity found to be 383 mAh/g.
- EXAMPLE 9 18.3 g MgV2 ⁇ s were used to make V2 ⁇ 5 » nH2 ⁇ as in Example 3, except a solution of 9.5 ml concentrated H2SO4 in 20 ml deionized water was added, and the H/N ratio was 2.1. The beaker was then removed from the heat and stirring discontinued. The solids settled quickly and were allowed to settle for 5 minutes. About 700 ml of supernatant liquid were decanted. The decanted supernatant liquid was pale yellow in color indicating the presence of some unprecipitated vanadium. About 700 ml of fresh H 2 O were added to the precipitate in the beaker, which was then slurried with the water by stirring for about one minute.
- the precipitate was allowed to settle for 10 minutes, and about 700 ml of the supernatant liquid were decanted.
- the washing/decanting step was repeated two more times.
- the pH of the supernatant liquid from the last wash was between 3 and 4.
- the product was easily and quickly collected on filter paper by suction filtration.
- the moist cake was crumbled onto a large cover glass and dried in air at room temperature for
- EXAMPLE 10 20.1 g of ⁇ H4VO3 were combined with 900 ml of deionized water and treated as in Example 1 to form V2 ⁇ 5 , nH2 ⁇ , except that a solution of 9.6 ml of concentrated H2SO4 in 25 ml deionized H2O was used, and the duration of heating after acid addition was 20 minutes.
- the H/V ratio was 2.
- Example 10 was repeated except that a solution of 9.6 ml of concentrated H2SO4 in 40 ml deionized H 2 O was used, and the duration of heating after acid addition was 60 minutes. The H/V ratio was 2. 15.4 g of product were recovered.
- a composition of ( ⁇ H4) 0- i2V2 ⁇ 5(S ⁇ 4)o.o6 ' 0.6H2 ⁇ was derived from a thermogravimetric analysis. On the basis of this composition, a product yield of 89% was calculated.
- An X-ray powder diffraction pattern showed only the lines ofV 2 O 5 ⁇ H2 ⁇ .
- Example 2 The resulting dried powder of V2 ⁇ 5 » nH2 ⁇ was then processed and combined as described in Example 1 to form an electrode 125 micrometers thick, which was incorporated into a coin cell as in Example 1, and the initial discharge capacity found to be 374 mAh/g.
- Example 7 was repeated, except that 30 ml of concentrated HNO3 were added, and the H/V ratio was 2.8. After washing and drying as in Example 7, 12.4 g of material were recovered.
- Example 2 The resulting dried powder of V ⁇ S'ILE ⁇ O was then processed and combined as described in Example 1 to form an electrode 115 micrometers thick, which was incorporated into a coin cell as in Example 1, and the initial discharge capacity found to be 350 mAh/g.
- Example 10 was repeated except that a solution of 19.2 ml of concentrated H 2 SO in 40 ml deionized H 2 O was used. The H/V ratio was 4. 13.6 g of product were recovered. A composition of (NH4)o.i2V2 ⁇ 5(S ⁇ 4)o.o6'lH2 ⁇ was derived from a thermogravimetric analysis. On the basis of this composition, a product yield of 76% was calculated. An X-ray powder diffraction pattern showed only the lines of V 2 O5'nH 2 O.
- Example 2 The resulting dried powder of N2 ⁇ 5 » nH2 ⁇ was then processed and combined as described in Example 1 to form an electrode 115 micrometers thick, which was incorporated into a coin cell as in Example 1, and the initial discharge capacity found to be 325 mAh/g.
- Example 3 was repeated, except that a solution consisting of 19.2 ml concentrated H2SO4 in 50 ml deionized H 2 O was added, and the duration of heating after acid addition was 20 minutes. The H/N ratio was 4. After washing and drying, 10.8 g of product were obtained. A product yield of 62% was estimated. An X-ray powder diffraction pattern showed only the lines of V 2 O 5 mH2 ⁇ .
- Example 2 The resulting dried powder of N2 ⁇ 5 » nH2 ⁇ was then processed and combined as described in Example 1 to form an electrode 98 micrometers thick, which was incorporated into a coin cell as in Example 1, and the initial discharge capacity found to be 321 mAh/g.
- Example 10 was repeated except that a solution of 28.8 ml of concentrated H2SO4 in 50 ml deionized H2O was used. The H/N ratio was 6. 9.6 g of product were recovered. A product yield of 55% was estimated. An X-ray powder diffraction pattern showed only the lines of N2 ⁇ 5 » nH2 ⁇ .
- Example 2 The resulting dried powder of V2 ⁇ 5 , nH 2 O was then processed and combined as described in Example 1 to form an electrode 105 micrometers thick, which was incorporated into a coin cell as in Example 1, and the initial discharge capacity found to be 272 mAh/g.
- EXAMPLE 16 20.1 g ⁇ H4VO3 was added to about 900 ml deionized H2O while stirring with a Teflon coated magnetic stirring bar in a 1 liter Pyrex beaker. The contents of the beaker were heated to the boiling point to form a solution. 1.56 g of
- the beaker was then removed from the heat and stirred for one hour. Solids were allowed to settle for 5 minutes. The warm supernatant liquid was decanted.
- the precipitate was re-slurried in a fresh aliquot of H2O for about one minute. The precipitate was again allowed to settle for about 10 minutes, and the supernatant liquid was decanted. A second aliquot of fresh water was added and the washing and solid separation process repeated. The washed, settled precipitate was collected on filter paper by suction filtration. The filter cake was chopped into small pieces and dried in air for about 64 hours, followed by drying under an IR heat lamp for four hours. An X-ray powder diffraction pattern showed only the lines of V2 ⁇ 5 # nH2 ⁇ .
- the powder was sieved through a 200 mesh screen to get powder suitable for making a cathode.
- the product was found by SEM to be non-fibrous up to 30,000x magnification.
- Electrodes were made using different binders. One electrode was made as described in Example 1 to form an electrode 120 micrometers thick, which was incorporated into a coin cell as in Example 1, and the initial discharge capacity found to be 350 mAh/g.
- the dried film consisting of 79.8% by weight active powder, 12.2% by weight binder, and 8% by weight carbon black, was hot-pressed through calendar rolls between Kapton® sheets at 2000 psi and 110°C to form a consolidated sheet suitable for use as a cathode in a lithium battery.
- the thickness of the sheet was 86 micrometers.
- Example 17 The electrode of Example 16 was employed as a cathode in a Li-ion electrochemical cell.
- the anode consisted of lithiated graphite that was formed in the coin cell by reacting at room temperature thin disks of Li metal and graphite. 6.0000 g of graphite powder MCMB25-28 (Osaka Gas Company, Japan) were combined with 0.1936 g of Super P carbon black ( MMM S.A. Carbon, Brussels, Belgium), and 6.452 g of a 4 wt % solution of EPDM rubber in cyclohexane. 2.0 ml extra cyclohexane were added to improve flow. The mixture was shaken in a capped glass vial for 15 minutes on a mechamcal shaker to form a graphite paste.
- the graphite paste was spread onto a sheet of Teflon® FEP (DuPont Company, Wilmington, DE) and drawn down to form a film using a doctor blade having a 40 mil gap. After drying, the film, consisting of 93% by weight graphite, 4% by weight binder, and 3% by weight carbon black, was hot-pressed in a calendar between Kapton® polyimide sheets (DuPont) at 2000 psi and 110°C to form a consolidated electrode sheet. The thickness of the sheet was about 295 micrometers.
- Disks of cathode, graphite, Li metal, and fiberglass separator were cut with punches, the graphite and Li metal in a glove box with a dry nitrogen atmosphere.
- the cathode and separator pieces were soaked in electrolyte solution consisting of LiPFg in EC/DMC (ethylene carbonate/dimethyl carbonate), then stacked along with two graphite disks and one Li disk, the Li disk having a thickness of about 100 micrometers, into a coin-cell pan and sealed under pressure using the 2325 Coin Cell Crimper System manufactured by the National Research Council of Canada.
- the coin cells were allowed to stand for 90 hours before testing.
- the quantities of graphite and Li metal gave a lithium-graphite composition of about LiCio which was believed to ensure that no Li metal would remain in the coin cell prior to testing.
- the coin cell was tested according to the standard method herein employed except that the voltage range was adjusted from 1.5-4.0 volts to
- Example 10 was repeated but the heated solution was cooled to room temperature before the acid was added. After 10 minutes, only a small amount of solid formed. More solid was observed after 1 hour, and even more solid formed after stirring overnight.
- the supernatant liquid was found to contain soluble, unprecipitated vanadium.
- the supernatantant liquid was decanted, and the solid was slurried with fresh deionized water by stirring for about one minute. The precipitate was allowed to settle for about 10 minutes.
- the pH of the supernatant liquid wash measured with multi-color strip pH paper, was 3. The washed, settled precipitate was collected on filter paper by suction filtration. The filter cake was chopped into small pieces and dried in air overnight. 14 g were obtained.
- EXAMPLE 19 20.1 g NH4VO3 were added to about 900 ml deionized H2O while stirring with a Teflon® coated magnetic stirring in a 1 liter Pyrex beaker. The contents of the beaker were heated to the boiling point to form a solution, followed by cooling the solution to room temperature. With stirring, 19.2 ml of concentrated H2SO4, diluted in 50 ml H2O, were added to the solution. The acid proton/vanadium ratio was 4. After 4 hours, only a trace amount of solid had formed.
- the reaction was held at about 45 °C overnight.
- the acid proton/vanadium ratio was 2.
- the supernatant liquid was found to contain some soluble, unprecipitated vanadium.
- the supernatatant liquid was decanted, and the solid was slurried with fresh deionized water by stirring for about one minute. The precipitate was allowed to settle for about 10 minutes.
- the pH of the supernatant liquid was, measured with multi-color strip pH paper, was 2-3. The washed, settled precipitate was collected on filter paper by suction filtration. The filter cake was chopped into small pieces and dried in air to give 15.8 g of product.
- X-ray powder diffraction showed the product to consist mainly of the desired material plus some (NH 4 ) 2 V 6 ⁇ i 6 .
- Example 2 The resulting dried mixed-phase powder was then processed and combined as described in Example 1 to form an electrode 120 um thick, which was incorporated into a coin cell as in Example 1, and the lithium capacity found to be 329 mAh/g, according to the method hereinabove described.
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Abstract
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JP2002534217A JP2004511407A (en) | 2000-10-07 | 2000-10-07 | Vanadium oxide hydrate composition |
AU2000279975A AU2000279975A1 (en) | 2000-10-07 | 2000-10-07 | Vanadium oxide hydrate compositions |
PCT/US2000/027660 WO2002030824A1 (en) | 2000-10-07 | 2000-10-07 | Vanadium oxide hydrate compositions |
EP00970624A EP1337468A1 (en) | 2000-10-07 | 2000-10-07 | Vanadium oxide hydrate compositions |
KR10-2003-7004845A KR20030059177A (en) | 2000-10-07 | 2000-10-07 | Vanadium Oxide Hydrate Compositions |
CN00819943A CN1454184A (en) | 2000-10-07 | 2000-10-07 | Vanadium oxide hydrate compositions |
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CN113451558A (en) * | 2021-06-28 | 2021-09-28 | 华南协同创新研究院 | Organic-inorganic hybrid material and preparation method and application thereof |
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2000
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Non-Patent Citations (4)
Title |
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DATABASE CHEMABS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; TOLSTOV, L. K. ET AL: "Hydrated vanadium pentoxide containing lithium", XP002169409, retrieved from STN Database accession no. 70:53456 CA * |
DATABASE CHEMABS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; TOLSTOV, L. K. ET AL: "Products of the hydrolytic precipitation of vanandium(V) in the lithium vanadate-nitric acid-water system", XP002169408, retrieved from STN Database accession no. 76:18531 CA * |
IZV. AKAD. NAUK SSSR, NEORG. MATER. (1968), 4(10), 1754-9, 1968 * |
TR. INST. KHIM., AKAD. NAUK SSSR, URAL. FILIAL (1970), NO. 20, 40-6, 1970 * |
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WO2015153485A1 (en) * | 2014-04-01 | 2015-10-08 | The Research Foundation For The State University Of New York | Electrode materials for group ii cation-based batteries |
US10763491B2 (en) | 2014-04-01 | 2020-09-01 | The Research Foundation For The State University Of New York | Low-temperature synthesis process of making MgzMxOy, where M is Mn, V or Fe, for manufacture of electrode materials for group II cation-based batteries |
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AU2000279975A1 (en) | 2002-04-22 |
WO2002030824A9 (en) | 2003-09-04 |
KR20030059177A (en) | 2003-07-07 |
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